Cross-linkable fluorinated photopolymer

ABSTRACT

A photosensitive composition is disclosed including a fluorinated photo cross-linkable polymer provided in a fluorinated solvent such as a hydrofluoroether. The photo cross-linkable polymer includes a first repeating unit having a fluorine-containing group but not a cinnamate group, and a second repeating unit having a fluorine-containing cinnamate group. The polymer has a total fluorine content in a range of 30 to 60% by weight. The composition can be used to form patterned barrier or dielectric structures over substrates and devices such as organic electronic devices.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. patent application Ser. No.15/117,032, filed on Aug. 5, 2016, which is a National Stage Applicationof PCT/US2015/014425 filed on Feb. 4, 2015, which claims priority toU.S. Patent Application Ser. No. 61/937,122, filed on Feb. 7, 2014, andwhich applications are incorporated herein by reference. A claim ofpriority is made to each of the above disclosed applications.

BACKGROUND

The present invention relates to fluorinated photopolymers having aphoto cross-linkable group. Such photopolymers are particularly usefulin organic electronic and bioelectronic devices.

Photocurable polymeric compositions have many possible commercialapplications. They can be used as dielectrics, insulators, encapsulants,inert overcoats, water or oil repellent layers, light blocking oremitting layers, paints, printing inks and the like. Certainphotocurable polymeric compositions are of particular use in thefabrication of organic electronic devices, including bioelectronicdevices.

Organic electronic devices may offer certain performance and priceadvantages relative to conventional inorganic-based devices. As such,there has been much commercial interest in the use of organic materialsin electronic device fabrication. For example, organic materials such asconductive polymers can be used to manufacture devices that have reducedweight and drastically greater mechanical flexibility compared toconventional electronic devices based on metals and silicon. Further,devices based on organic materials are likely to be less damaging to theenvironment than devices made with inorganic materials, since organicmaterials do not require toxic metals and can ideally be fabricatedusing relatively benign solvents and methods of manufacture. Thus, inlight of these superior weight and mechanical properties, andparticularly in light of the lowered environmental impact in fabricationand additionally in disposal, electronic devices based on organicmaterials are expected to be less expensive than devices based onconventional inorganic materials.

One problem facing bioelectronic and organic electronic devices is thatthe materials and patterning processes used for conventional inorganicelectronics are often not compatible with biological and organicelectronic materials. Thus, new materials and processes are needed. Forexample, electronic devices usually require an insulating or dielectriclayer (e.g., SiO₂ or spin-coated polymers). Typical insulating ordielectric materials and processing methods are often not compatiblewith sensitive bioelectronic and organic electronic material layers.Further, many organic electronic devices contain materials that aremoisture or air sensitive and require special encapsulation methods orcoatings.

US 2011/0159252 discloses a useful method for patterning organicelectronic materials by an “orthogonal” process that uses fluorinatedsolvents and fluorinated photoresists. The fluorinated solvents havevery low interaction with organic electronic materials. However, thedisclosed fluorinated photoresists are generally not designed to form apermanent layer in a device, but rather, are removed.

In light of the above, there is a need to provide a more effectivedielectric and barrier layer materials, structures and methods that arecompatible in bioelectronic and organic electronic devices.

SUMMARY

In accordance with one aspect of the present disclosure, aphotosensitive composition includes a fluorinated solvent and afluorinated photo cross-linkable polymer including at least onerepeating unit having a fluorine-containing cinnamate group, wherein thepolymer has a total fluorine content in a weight range of 20 to 60%.

In accordance with another aspect of the present disclosure, aphotosensitive composition includes a fluorinated solvent and afluorinated photo cross-linkable polymer including a first repeatingunit having fluorine-containing group but not a cinnamate group, and asecond repeating unit having a fluorine-containing cinnamate group,wherein the polymer has a total fluorine content in a weight range of 30to 60%.

In accordance with another aspect of the present disclosure, aphotosensitive composition includes a hydrofluoroether solvent and afluorinated photo cross-linkable polymer including at least a firstrepeating unit having a fluorine-containing group and a second repeatingunit having a cinnamate group; and a hydrofluoroether solvent.

In accordance with another aspect of the present disclosure, a method ofprocessing a fluorinated photo cross-linkable polymer includes: forminga photopolymer layer on a substrate, the photopolymer layer including aphoto cross-linkable polymer according to any of the photosensitivecompositions of the present disclosure; exposing the photopolymer layerto patterned radiation to form an exposed photopolymer layer; andcontacting the exposed photopolymer layer with a developing agent toremove a portion of the exposed photopolymer layer in accordance withthe patterned light, thereby forming a developed structure having afirst pattern of cross-linked polymer covering the substrate and acomplementary second pattern of uncovered substrate corresponding to theremoved portion of polymer, the developing agent including at least 50%by volume of a fluorinated developing solvent.

In accordance with another aspect of the present disclosure, a method offorming a dielectric structure includes: providing a first photopolymerlayer over a substrate, the first photopolymer layer including a firstphoto cross-linkable polymer having at least a first repeating unithaving a fluorine-containing group, a second repeating unit having aphoto cross-linkable group and a third repeating having adry-etch-resistant group including at least one dry-etch-resistant atomhaving an atomic weight of at least 24; exposing the first photopolymerlayer to radiation to form a cross-linked first polymer; and subjectingthe cross-linked first polymer to a dry etching gas to form a firstdielectric structure having a surface region comprising a higher densityof dry-etch-resistant atoms than an interior region.

In an embodiment, cross-linked thin films formed from compositions ofthe present disclosure have high resistance to water and organicsolvents. In an embodiment, cross-linked thin films of the presentdisclosure form effective dielectric layers in electronic devices. In anembodiment, cross-linked films of the present disclosure are used toform multi-layer protective barriers over water- or oxygen-sensitiveelectronic devices. In certain embodiments, surface wettability of thecross-linked films or the coatability of subsequent layers may betailored to specific needs by selecting the amount of polymer branchingor fluorine content.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a flow chart depicting the steps for forming a developedstructure according to an embodiment of the present disclosure;

FIG. 2A is a cross-sectional view of a bottom gate/bottom contactorganic thin film transistor according to an embodiment of the presentdisclosure;

FIG. 2B is a cross-sectional view of a bottom gate/top contact organicthin film transistor according to an embodiment of the presentdisclosure;

FIG. 2C is a cross-sectional view of a top gate/bottom contact organicthin film transistor according to an embodiment of the presentdisclosure;

FIG. 2D is a cross-sectional view of a top gate/top contact organic thinfilm transistor according to an embodiment of the present disclosure;

FIG. 3 is a flow chart depicting the steps for forming a dielectricstructure according to an embodiment of the present disclosure;

FIG. 4A through 4D illustrates a series of cross-sectional views atvarious stages of forming a dielectric structure according to anembodiment of the present disclosure; and

FIG. 5 is a cross-sectional diagram of an OTFT device having first andsecond dielectric structures.

DETAILED DESCRIPTION

It is to be understood that the attached drawings are for purposes ofillustrating the concepts of the invention and may not be to scale.

A photosensitive composition (also referred to herein as a photopolymercomposition) includes a light-sensitive material that can be coated orapplied in some way to produce a photocurable film, e.g., aphoto-patternable film. In a preferred embodiment, photopolymers of thepresent disclosure remain as part of a device and may be used to formvarious layers or structures as discussed more fully below. Anembodiment of the present disclosure is directed to improved fluorinatedphotopolymers that are particularly suited for coating and developingusing fluorinated solvents. The solvents for the fluorinatedphotopolymer solution and developing agent are each chosen to have lowinteraction with other material layers that are not intended to bedissolved or otherwise damaged. Such solvents are collectively termed“orthogonal” solvents. This can be tested by, for example, immersion ofa device including the material layer of interest into the solvent priorto operation. The solvent is orthogonal if there is no problematicreduction in the functioning of the device.

Certain embodiments of the present disclosure are particularly suited todevices using solvent- or water-sensitive, active organic materials.Examples of active organic materials include, but are not limited to,organic electronic materials, such as organic semiconductors, organicconductors, OLED (organic light-emitting diode) materials and organicphotovoltaic materials, organic optical materials and biologicalmaterials (including bioelectronic materials). Many of these materialsare easily damaged when contacted with organic or aqueous solutions usedin conventional photolithographic processes. Active organic materialsare often coated to form a layer that may be patterned. For some activeorganic materials, such coating can be done from a solution usingconventional methods. Alternatively, some active organic materials arecoated by vapor deposition, for example, by sublimation from a heatedorganic material source at reduced pressure. Solvent-sensitive, activeorganic materials can also include composites of organics andinorganics. For example, the composite may include inorganicsemiconductor nanoparticles (quantum dots). Such nanoparticles may haveorganic ligands or be dispersed in an organic matrix.

The photopolymers of the present disclosure are provided in a coatingsolvent that typically includes at least 50% by volume of a fluorinatedsolvent, preferably at least 90% by volume. If a deposited layer isintended to be photo-patterned, a pattern-exposed photopolymer layer canbe developed using a developing agent capable of discriminating betweenexposed and unexposed areas. In an embodiment, the developing agentincludes at least 50% by volume of a fluorinated solvent, preferably atleast 90% by volume. In an embodiment, a developed (patterned)photopolymer layer may optionally be stripped using a stripping agentcapable of dissolving or lifting off the exposed photopolymer. In anembodiment, the stripping agent includes at least 50% by volume of afluorinated solvent. Depending on the particular material set andsolvation needs of the process, the fluorinated solvent may be selectedfrom a broad range of materials such as chlorofluorocarbons (CFCs),hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs),perfluorocarbons (PFCs), hydrofluoroethers (HFEs), perfluoroethers,perfluoroamines, trifluoromethyl-substituted aromatic solvents,fluoroketones and the like.

Particularly useful fluorinated solvents include those that areperfluorinated or highly fluorinated liquids at room temperature, whichare immiscible with water. Among those solvents, hydrofluoroethers(HFEs) are known to be highly environmentally friendly, “green”solvents. HFEs, including segregated HFEs, are preferred solventsbecause they are non-flammable, have zero ozone-depletion potential,lower global warming potential than PFCs and show very low toxicity tohumans.

Examples of readily available HFEs and isomeric mixtures of HFEsinclude, but are not limited to, an isomeric mixture of methylnonafluorobutyl ether and methyl nonafluoroisobutyl ether (HFE-7100), anisomeric mixture of ethyl nonafluorobutyl ether and ethylnonafluoroisobutyl ether (HFE-7200 aka Novec™ 7200),3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane(HFE-7500 aka Novec™ 7500),1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3,-hexafluoropropoxy)-pentane(HFE-7600 aka PF7600 (from 3M)), 1-methoxyheptafluoropropane (HFE-7000),1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-trifluoromethylpentane(HFE-7300 aka Novec™ 7300), 1,2-(1,1,2,2-tetrafluoroethoxy)ethane(HFE-578E), 1,1,2,2-tetrafluoroethyl-1H,1H,5H-octafluoropentyl ether(HFE-6512), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether(HFE-347E), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(HFE-458E),2,3,3,4,4-pentafluorotetrahydro-5-methoxy-2,5-bis[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-furan(HFE-7700 aka Novec™ 7700) and1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane-propyl ether (TE6O-C3).

Coatable, fluorinated photopolymer compositions useful in the presentdisclosure include a fluorinated solvent and a fluorinated photopolymer(homopolymer or copolymer) material having photo cross-linkablerepeating units, and optionally, other repeating units having otherfunctional groups such as photosensitizing groups, light-absorbinggroups, etch-resistant groups, solubility or rheology-modifying groups,adhesion-promoting groups, dielectric-modifying groups, Tg-modifyinggroups, branching agents and the like. The terms polymer and copolymerin the present disclosure includes oligomers in addition to higher MWpolymers. A copolymer is suitably a random copolymer, but othercopolymer types can be used, e.g., block copolymers, alternatingcopolymers, periodic copolymers and branched copolymers. The term“repeating unit” is used broadly herein and simply means that there ismore than one unit per polymer chain. The term is not intended to conveythat there is necessarily any particular order or structure with respectto the other repeating units unless specified otherwise.

Preferred fluorinated photopolymers of the present disclosure generallyhave a total fluorine content in a weight range of about 15 to 60%. Inan embodiment, the fluorinated photopolymer is soluble in at least onehydrofluoroether solvent to at least 1% by weight, preferably to atleast 5% by weight, and more preferably to at least 10% by weight. In anembodiment, the fluorinated photopolymer composition solvent(s) arecomprised of at least 50% by volume of a hydrofluoroether solvent havinga boiling point in a range of 100° C. to 175° C., or preferably 100° C.to 150° C., as such solvents often provide improved coatings relative tosolvents outside of this range. The photosensitive composition mayoptionally include various additives such as sensitizing dyes,stabilizers, coating aids, and the like, so long as they have sufficientsolubility or dispersability in fluorinated solvents, particularlyhydrofluoroethers, to maintain desired functionality.

When the fluorinated photopolymer composition (e.g., as a dried layerprovided on a substrate) is exposed to radiation such as UV or visiblelight, the photo cross-linkable group cross-links with another photocross-linkable group, e.g., on another chain of fluorinatedphotopolymer. This significantly reduces its solubility relative to theunexposed regions thereby allowing development of an image with theappropriate solvent (typically fluorinated). In an embodiment, thereduced solubility of radiation-exposed photopolymer can be used to forma permanent layer or structure in a device.

Photopolymers of the present disclosure may be formed by many possiblemethods known in the art. For example, photo cross-linkable repeatingunits (and other repeating units if desired) may be formed via apost-polymerization reaction. In such method, an intermediate polymer (aprecursor to the desired photopolymer) is first prepared, saidintermediate polymer comprising suitably reactive functional groups forforming one of more of the desired repeating units. For example, anintermediate polymer containing pendant carboxylic acid moieties can bereacted with a target compound bearing an alcohol group in anesterification reaction to produce the desired repeating unit. Inanother example, a polymer containing a suitable leaving group such asprimary halide can be reacted with a target compound bearing a phenolmoiety to form a repeat unit via an etherification reaction. In additionto simple condensation reactions such as esterification and amidation,and simple displacement reactions such as etherification, a variety ofother covalent-bond forming reactions well-known to practitionersskilled in the art of organic synthesis can be used to form any of thespecified repeat units. Examples include palladium-catalyzed couplingreactions, “click” reactions, addition to multiple bond reactions,Wittig reactions, reactions of acid halides with suitable nucleophiles,and the like.

Alternatively, the repeating units of the photopolymer are formeddirectly by polymerization of one or more appropriate monomers, ratherthan by attachment to an intermediate polymer. That is, monomers havinga polymerizable group and the desired repeating unit are polymerized.Some non-limiting examples of useful polymerizable groups includeacrylates (e.g. acrylate, methacrylate, cyanoacrylate and the like),acrylamides, vinylenes (e.g., styrenes), vinyl ethers and vinyl estersAlthough many of the embodiments below refer to polymerizable monomers,analogous structures and ranges are contemplated and within the scope ofthe present disclosure, wherein one or more of the repeating units areinstead formed by attachment of the relevant group to an intermediatepolymer as described above.

In an embodiment, a photosensitive composition includes a photocross-linkable polymer comprising at least a repeating unit having afluorine-containing cinnamate group, wherein the polymer has a totalfluorine content in a weight range of 20 to 60%, preferably 30 to 55%,and further comprises a fluorinated solvent, preferably ahydrofluoroether. The photo cross-linkable polymer of this embodimentmay comprise a repeating unit having a fluorine-containing cinnamategroup as shown in formula (1):

wherein p is an integer from 1 to 5, X is an independently selectedfluorine-containing alkyl, alkoxy, alkylthio, aryl, aryloxy, alkanoate,benzoate, alkyl ester, aryl ester, or alkanone; q is an integer from 0to 4 such that q+p≤5, Z is an independently selected alkyl, alkoxy,alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester,or alkanone; and “poly” represents a polymer chain including anyoptional linking groups between the fluorinated cinnamate group and thepolymer chain. Throughout this disclosure, unless otherwise specified,any use of the term alkyl includes straight-chain, branched and cycloalkyls. In certain embodiments, the weight percentage of the structureaccording to formula (1), not including “poly”, accounts for at least25% of the total polymer weight. The fluorine-containing cinnamate groupmay optionally be the only repeating unit of the photo cross-linkablepolymer, but alternatively, additional repeating units bearing otherfunctional groups (mentioned above) may optionally be included alongwith the fluorine-containing cinnamate. In an embodiment, the additionalrepeating unit includes an alkyl-containing group. In certainembodiments, the mole percentage of repeating unit comprising thefluorinated cinnamate group relative to all repeating units is in arange of 25 to 100%.

Some non-limiting examples of polymerizable monomers in accordance withformula (1) are shown below.

In an embodiment, a photosensitive composition includes a fluorinatedphoto cross-linkable polymer comprising a first repeating unit having afluorine-containing group but not a cinnamate group, and a secondrepeating unit having a fluorine-containing cinnamate group, wherein thepolymer has a total fluorine content in a weight range of 30 to 60%,preferably 35 to 55%, and further comprises a fluorinated solvent,preferably a hydrofluoroether. For example, the photo cross-linkablepolymer of this embodiment may comprise a repeating unit having afluorine-containing cinnamate group as shown in formula (1) above. Inthis embodiment, the mole ratio of the first repeating unit to thesecond repeating unit is typically in a range of 0.1 to 10, oralternatively, 0.25 to 4.

The first repeating unit having the fluorine-containing group but not acinnamate group is preferably a fluorine-containing alkyl, alkoxy,alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester,or alkanone. In an embodiment, the fluorine-containing group is ahydrofluorocarbon or hydrofluoroether having at least as many fluorineatoms as carbon atoms. In an embodiment, the fluorine-containing groupis a perfluorinated alkyl or a partially fluorinated alkyl group havingat least 4 carbon atoms, including but not limited to1H,1H,2H,2H-perfluoroalkyls such as 1H,1H,2H,2H-perfluorooctyl (i.e.,2-perfluorohexyl ethyl).

In an embodiment, the fluorinated photopolymer material includes acopolymer comprising at least two distinct repeating units, including afirst repeating unit having a fluorine-containing group, and a secondrepeating unit having a photo cross-linkable group. In certainalternative embodiments, the cross-linkable group may be acid- orbase-catalyzed, or directly photo cross-linkable. Acid catalyzedcross-linkable groups are discussed in more detail below. In anembodiment, the photo cross-linkable group is directly cross-linkablewithout the need for acid or base catalysis. Directly photocross-linkable groups work by forming a photo excited state (either bydirect absorption of light or by energy transfer from a sensitizing dye)that cross-links with another cross-linkable group, e.g., on anotherchain of polymer. There are many directly photo cross-linkable groupsknown in the art. In an embodiment, the directly photo cross-linkablegroup comprises a cross-linkable carbon-carbon double bond.

In an embodiment, a photosensitive composition includes a photocross-linkable polymer comprising at least a first repeating unit havingfluorine-containing group and a second repeating unit having a cinnamategroup, and a hydrofluoroether solvent. In an embodiment, the polymer hasa total fluorine content in a weight range of 15 to 55%, preferably 20to 50%, or more preferably 25 to 45%. The first repeating unit includesthose described previously with respect to a first repeating unit havinga fluorine-containing group but not a cinnamate group.

In a preferred embodiment, the photo cross-linkable group comprises acinnamate, e.g., as shown in formula (2):

wherein p is an integer from 0 to 5, X is an independently selectedfluorine-containing alkyl, alkoxy, alkylthio, aryl, aryloxy, alkanoate,benzoate, alkyl ester, aryl ester, or alkanone; q is an integer from 0to 5 such that q+p≤5, Z is an independently selected alkyl, alkoxy,alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester,or alkanone; and “poly” represents a polymer chain including anyoptional linking groups between the cinnamate group and the polymerchain. Some non-limiting examples of polymerizable monomers inaccordance with formula (2) include the materials shown above withrespect to formula (1), C-1 through C-6, and those shown below.

In an embodiment, p and q are both 0. In another embodiment, q is 0, pis at least 1 and X is a fluorine-containing alkyl or alkoxy. In anotherembodiment, q and p are both at least 1, X is a fluorine-containingalkyl or alkoxy, and Z is a non-fluorine-containing alkyl or alkoxy. Inan embodiment, when at least one or both of q and p is at least 1, thephotopolymer composition does not include a sensitizing dye. In anembodiment, when q and p are both 0, the photopolymer compositionincludes a sensitizing dye.

In an embodiment, the mole ratio of the first repeating unit to thesecond repeating unit is in a range of 0.1 to 10, or alternatively, in arange of 0.25 to 4.

In an embodiment, the fluorinated photopolymer material includes acopolymer formed at least from a first monomer having afluorine-containing group and a second monomer having a photocross-linkable group. Additional monomers may optionally be incorporatedinto the copolymer. The first monomer is one capable of beingcopolymerized with the second monomer and has at least onefluorine-containing group.

In an embodiment, the fluorine-containing group of the first monomer isan alkyl or aryl group that may optionally be further substituted withchemical moieties other than fluorine, e.g., chlorine, a cyano group, ora substituted or unsubstituted alkyl, alkoxy, alkylthio, aryl, aryloxy,amino, alkanoate, benzoate, alkyl ester, aryl ester, alkanone,sulfonamide or monovalent heterocyclic group, or any other substituentthat a skilled worker would readily contemplate that would not adverselyaffect the performance of the fluorinated photopolymer. In anembodiment, the first monomer does not contain protic or chargedsubstituents, such as hydroxy, carboxylic acid, sulfonic acid or thelike. In a preferred embodiment, the first monomer has a structureaccording to formula (3):

In formula (3), R₁ represents a hydrogen atom, a cyano group, a methylgroup or an ethyl group. R₂ represents a fluorine-containing group, inparticular, a substituted or unsubstituted alkyl group having at least 1fluorine atom, preferably at least 3 fluorine atoms and more preferablyat least 5 fluorine atoms. In an embodiment, the alkyl group is ahydrofluorocarbon or hydrofluoroether having at least as many fluorineatoms as carbon atoms. In an embodiment R₂ represents a perfluorinatedalkyl or a partially fluorinated alkyl group having at least 4 carbonatoms, including but not limited to 1H,1H,2H,2H-perfluorinated alkylhaving at least 4 carbon atoms. An example of the latter would be1H,1H,2H,2H-perfluorooctyl (i.e., 2-perfluorohexyl ethyl), and aparticularly useful first monomer includes 1H,1H,2H,2H-perfluorooctylmethacrylate (“FOMA”) and similar materials.

In an embodiment, the photo cross-linkable group of a copolymer is anacid-catalyzed cross-linkable group. Activation of the acid-catalyzedcross-linkable group typically requires that a photo-acid generator(PAG) be added to the fluorinated photopolymer composition, e.g., as asmall molecule additive. If there is no additional sensitizing dye, thePAG absorbs radiation such as UV or visible light to initiate anacid-forming decomposition reaction. In some embodiments, thecomposition includes a sensitizing dye, either added to the solution orincorporated into the polymer. In this case, the sensitizing dye absorbsradiation and forms an excited state capable of reacting with a PAG togenerate an acid. The acid catalyzes the cross-linking of theacid-catalyzed cross-linkable groups, e.g., between two polymer chains.In some cases the radiation-exposed photopolymer may need to be heatedfor a short time to catalyze cross-linking. Chemically amplified systemssuch as this can be desirable in certain embodiments since they enablethe exposing step to be performed through the application of relativelylow energy UV light exposure (typically under 100 mJ/cm²). This isadvantageous since some active organic materials useful in applicationsto which the present disclosure pertains may partially decompose in thepresence of intense UV light. Also, decreased light exposure may beobtained by shorter exposure duration, improving the manufacturingthroughput of the desired devices.

Examples of acid-catalyzed cross-linkable groups include, but are notlimited to, cyclic ether groups and vinyloxy groups. In an embodiment,the cyclic ether is an epoxide or an oxetane. Some non-limiting examplesof some acid-catalyzed cross-linkable groups include the followingwherein (*) refers to an attachment site to the photopolymer orpolymerizable group:

Many useful PAG compounds exist that may be added to a photopolymercomposition. The PAG preferably has at least some solubility in thecoating solvent. The amount of PAG required depends upon the particularsystem, but generally, will be in a range of 0.1 to 6% by weightrelative to the photopolymer. In some embodiments, the presence of asensitizing dye in the composition may substantially reduce the amountof PAG required. In an embodiment, the amount of PAG is in a range of0.1 to 2% relative to the photopolymer. Fluorinated PAGs are generallypreferred and non-ionic PAGs are particularly useful. Some usefulexamples of PAG compounds include2-[2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxyimino)-pentyl]-fluorene(ONPF) and2-[2,2,3,3,4,4,4-heptafluoro-1-(nonafluorobutylsulfonyloxyimino)-butyl]-fluorene(HNBF). Other non-ionic PAGS include: norbornene-based non-ionic PAGssuch as N-hydroxy-5-norbornene-2,3-dicarboximideperfluorooctanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximideperfluorobutanesulfonate, and N-hydroxy-5-norbornene-2,3-dicarboximidetrifluoromethanesulfonate; and naphthalene-based non-ionic PAGs such asN-hydroxynaphthalimide perfluorooctanesulfonate, N-hydroxynaphthalimideperfluorobutanesulfonate and N-hydroxynaphthalimidetrifluoromethanesulfonate.

Some additional classes of PAGs include: triarylsulfoniumperfluoroalkanesulfonates, such as triphenylsulfoniumperfluorooctanesulfonate, triphenylsulfonium perfluorobutanesulfonateand triphenylsulfonium trifluoromethanesulfonate; triarylsulfoniumhexafluorophosphates (or hexafluoroantimonates), such astriphenylsulfonium hexafluorophosphate and triphenylsulfoniumhexafluoroantimonate; triaryliodonium perfluoroalkanesulfonates, such asdiphenyliodonium perfluorooctanesulfonate, diphenyliodoniumperfluorobutanesulfonate, diphenyliodonium trifluoromethanesulfonate,di-(4-tert-butyl)phenyliodonium, perfluorooctanesulfonate,di-(4-tert-butyl)phenyliodonium perfluorobutanesulfonate, anddi-(4-tert-butyl)phenyliodonium trifluoromethanesulfonate; andtriaryliodonium hexafluorophosphates (or hexafluoroantimonates) such asdiphenyliodonium hexafluorophosphate, diphenyliodoniumhexafluoroantimonate, di-(4-tert-butyl)phenyliodoniumhexafluorophosphate, and di-(4-tert-butyl)phenyliodoniumhexafluoroantimonate. Suitable PAGs are not limited to thosespecifically mentioned above. Combinations of two or more PAGs may beused as well.

It is common in photolithography to etch patterns into layers using a“dry etchant” with the patterned photopolymer acting as an etch barrier.Herein, the term “dry etchant” is used broadly and refers to any usefulgaseous material possessing energy sufficient to etch (remove) a targetmaterial. Dry etching includes, but is not limited to, glow dischargemethods (e.g., sputter etching and reactive ion etching), ion beametching (e.g., ion milling, reactive ion beam etching, ion beam assistedchemical etching) and other “beam” methods (e.g., ECR etching anddownstream etching), all of which are methods known in the art. Somecommon dry etchants include oxygen plasma, argon plasma, UV/ozone, CF₄and SF₆, and various combinations.

It can be advantageous, therefore, for the photopolymer to havereasonable resistance to the dry etch to ensure good pattern transfer tothe underlying layer. The fluorinated photopolymer may optionallycomprise a repeating unit having a dry-etch-resistant group. Polycyclicorganic groups are sometimes used to improve dry-etch resistance.Alternatively, or in addition, the dry-etch-resistant group includes atleast one dry-etch-resistant atom having an atomic weight of at least24. In an embodiment, the dry-etch-resistant atom is Si, Ti, Ge, Al, Zr,or Sn. The dry-etch-resistant group may optionally be formed from apolymerizable monomer, e.g., one that has an organosilane, a siloxane,silazane or metalloxane group. In a preferred embodiment, thedry-etch-resistant group includes a silane or siloxane group. In certainembodiments, when a fluorinated photopolymer layer is subjected to anetching gas comprising oxygen radicals, the dry-etch-resistant groupwill break down to form a layer of oxide, e.g., silicon oxide (SiOx) orother metal oxide. This layer of oxide reduces the etch rate of theremaining underlying polymer and can be used to form a dielectricstructure having a surface region comprising a higher density ofdry-etch-resistant atoms than an interior region.

Some non-limiting examples of polymerizable monomers having adry-etch-resistant group include those that have a structure accordingto formula (3):

In formula (3), R₁ through R₃ are independently selected alkyl, aryl,alkoxy, aryloxy, siloxy groups, a=0 or 1, L is an optional linking groupconnecting a polymerizable vinyl moiety to the Si atom. The vinyl moietymay be have additional substitution so long as it is still readilypolymerizable, e.g., alkyl, fluoro or cyano groups, or it may be part ofa ring structure, e.g., as in norbornene or adamantane. A fewnon-limiting examples of such structures include:

In an embodiment, the dry-etch-resistant group is provided as part of athird repeating unit in a fluorinated photopolymer also comprising afirst repeating unit having a fluorine-containing group and a secondrepeating unit having a photo cross-linkable group. In an embodiment,the mole ratio of the third repeating unit relative to the combinedfirst and second repeating units is in a range of 0.1 to 1.

In an embodiment, the fluorinated photopolymer of the present disclosureincludes sensitizing dye (in solution or attached to the polymer) thathas a light absorption peak in a range of 300 to 450 nm as measured in adeposited film or in a fluorinated solvent solution. Although otherwavelengths can be used, this range is compatible with many of thephotolithographic, mercury lamp exposure units available in the industrythat use i-line, h-line or g-line exposures.

Some non-limiting examples of potentially useful sensitizing dyes forcinnamate cross-linking groups include diaryl ketones (e.g.,benzophenones), arylalkyl ketones (e.g., acetophenones), diarylbutadienes, diaryl diketones (e.g. benzils), xanthones, thioxanthones,naphthalenes, anthracenes, benzanthrone, phenanthrenes, chrysene,anthrones, 5-nitroacenapthene, 4-nitroaniline, 3-nitrofluorene,4-nitromethylaniline, 4-nitrobiphenyl, picramide,4-nitro-2,6-dichlorodimethylaniline, Michler's ketone,N-acyl-4-nitro-1-naphthylamine.

Preparation and polymerization of the monomers discussed above cangenerally be achieved using standard synthetic methods known to askilled artisan. Some useful examples of the preparation of orthogonalphotopolymers can be found in US Publication No. 2011/0159252, PCTpublication WO2012148884, and co-pending U.S. application Ser. Nos.14/291,692, 14/291,767, 14/335,406 and 14/539,574, the entire contentsof which are incorporated herein by reference. Examples of thepreparation of polymers incorporating acid-catalyzed cross-linkablegroups can be found in US Publication Nos. 2009/0263588, 2009/0130591,and 2002/0161068, the entire contents of which are incorporated byreference. Examples of fluorinated copolymers comprising cinnamates canbe found in U.S. Pat. No. 4,529,783.

A fluorinated photosensitive composition of the present disclosure maybe applied to a substrate using any method suitable for depositing aphotosensitive liquid material. For example, the composition may beapplied by spin coating, curtain coating, bead coating, bar coating,spray coating, dip coating, gravure coating, ink jet, flexography or thelike. The composition may be applied to form a uniform film or apatterned layer of unexposed photopolymer. Alternatively, thephotopolymer can be applied to the substrate by transferring a preformedfluorinate photopolymer layer (optionally patterned) from a carriersheet, for example, by lamination transfer using heat, pressure or both.In such an embodiment, the substrate or the preformed photopolymer layermay optionally have coated thereon an adhesion promoting layer.

A flow diagram for a photopatterning embodiment of the presentdisclosure is shown in FIG. 1, and includes the step 2 of forming aphotopolymer layer on a substrate. The substrate may optionally be amultilayer structure having a rigid or flexible support (e.g., glass orplastic) and one or more additional patterned or non-patterned layers(e.g., made from dielectric materials, conductors, semiconductors,optically active materials and the like). In an embodiment, the top ofthe substrate includes a layer of active organic material that is indirect contact with the photopolymer layer.

In step 4 the photopolymer layer is exposed to patterned radiationwithin the spectral sensitivity range of the photopolymer (e.g., lightin a range of 300 nm to 450 nm), thereby forming an exposed photopolymerlayer having both exposed and unexposed portions. The patternedradiation forms areas of differential developability due to somechemical or physical change caused by the radiation exposure. In thepresent disclosure, radiation causes cross-linkable groups to react andcross link. Such cross linking generally reduces solubility in typicaldeveloper solutions, thus, the photopolymer layer is generally anegative tone material. Patterned radiation can be produced by manymethods, for example, by directing exposing light through a photomaskand onto the photopolymer layer. Photomasks are widely used inphotolithography and often include a patterned layer of chrome thatblocks light. The photomask may be in direct contact or in proximity.When using a proximity exposure, it is preferred that the light has ahigh degree of collimation. Alternatively, the patterned light can beproduced by a projection exposure device. In addition, the patternedlight can be from a laser source that is selectively directed to certainportions of the photopolymer layer.

In step 6, a developed structure is formed that includes a first patternof exposed photopolymer. This can be done by contacting the exposedphotopolymer layer to a developing agent. In an embodiment, thedeveloping agent includes at least 50% by volume of a fluorinatedsolvent, e.g., a hydrofluoroether (HFE) solvent. During development, theportions of unexposed photopolymer are removed, thus forming a developedstructure having a first pattern of exposed photopolymer that covers thesubstrate and a complementary second pattern of uncovered substratecorresponding to the removed portion of photopolymer. By “uncoveredsubstrate”, it is meant that the surface of the substrate issubstantially exposed or revealed to a degree that it can be subjectedto further treatments. Contacting the exposed photopolymer layer can beaccomplished by immersion into the developing agent or by coating itwith the developing agent in some way, e.g., by spin coating or spraycoating. The contacting can be performed multiple times if necessary.The developed structure may optionally be subjected to further steps,depending on the nature of the device. For example, the structure may betreated in some way to modify a property of the uncovered substrate orexposed photopolymer, coated with an additional material layer, ortreated with a wet or dry etch to remove a portion of the uncoveredsubstrate.

In an embodiment, the fluorinated photopolymer of the present disclosureis used as a gate dielectric material in a thin film transistor (TFT),preferably an organic thin film transistor (OTFT). General materials andmethods for making and operating OTFT devices are known to the skilledartisan, and some non-limiting examples can be found in U.S. Pat. Nos.7,029,945, 8,404,844, 8,334,456, 8,411,489 and 7,858,970, the entirecontents of which are incorporated by reference. FIGS. 2A-2D illustratea few of the numerous possible embodiments, but in general, an OTFT isformed on a substrate 10 and has an organic semiconductor material layer12, a gate dielectric material layer 14, a source electrode 16, a drainelectrode 18 and a gate electrode 20. FIG. 2A shows a bottom gate/bottomcontact OTFT, FIG. 2B shows a bottom gate/top contact OTFT, FIG. 2Cshows a top gate/bottom contact OTFT, and FIG. 2D shows a top gate/topcontact OTFT. In a preferred embodiment, the photopolymer is used as adielectric in a top gate OTFT device. When used in displays, an array ofOTFTs is typically provided in order to individually address eachdisplay pixel or sub-pixel. Although not shown in FIGS. 2A-2D, gatedielectric material layer 14 may be photopatterned as needed, forexample, to provide open areas for making electrical contacts orbuilding via structures. In addition, although not shown in FIGS. 2A-2D,the organic semiconductor material layer may be patterned so that eachOTFT or display pixel/sub-pixel has its own discrete and separateorganic semiconductor material.

The fluorinated photopolymer of the present disclosure may be used as anelectrically insulating layer in an electronic device. For example, itmay act as an insulating layer in a wire, a TFT structure (besides or inaddition to acting as a gate dielectric), a touch screen, an RFIDdevice, a sensor, a capacitor, a photovoltaic device, bioelectronicdevice and the like.

The present fluorinated photopolymer may be used as a partitionstructure that separates light-emitting areas of a display or lightingdevice, e.g., as described in U.S. Pat. No. 6,693,296 or in U.S. Pat.No. 5,701,055, the entire contents of both patents are incorporated byreference herein. Some examples of useful light-emitting materialsinclude organic light-emitting materials, such as those used in OLEDdevices, and semiconductor nanoparticles, such as quantum dots formedfrom colloidal semiconductor nanocrystals, particularly III/V or II/VIsemiconductors.

The present fluorinated photopolymer may be patterned to form aplurality of wells that may be used for many possible purposes. e.g.,wells that are capable of containing a display material. For example,the fluorinated photopolymer may form banks and wells as described in US2005/0196969, the entire contents of which are incorporated byreference, wherein the wells are filled with a solution-based organiclight emitting material. Such filling can optionally be by ink jet.Alternative display materials that may be added include liquid crystalmaterial, electrophoretic material, a semiconductor nanoparticlematerial, a color filter material, and the like.

The present fluorinated photopolymer may be used to form at least aportion of a barrier layer in a water- or solvent-sensitive device.Organic semiconductors and organic light-emitting materials inparticular are often very sensitive to water. A barrier layer can becoated over a device as a single layer or as multiple layers and mayoptionally be part of an alternating photopolymer/inorganic oxidemultilayer barrier structure. In an embodiment, the water vaportransmission rate through a barrier layer comprising the presentfluorinated photopolymer is less than 10⁻⁵ g/m²/day, preferably lessthan 10⁻⁶ g/m²/day, under ambient temperature and humidity conditions.In an embodiment, the water vapor transmission rate through a barriercomprising the present fluorinated photopolymer is less than 10.2g/m²/day, preferably less than 10 g/m²/day, in an accelerated test at60° C./90% RH (relative humidity). Tests for measuring water vaportransmission rates are known in the art, an example of which can befound in Organic Electronics 14 (2013) 3385-3391.

A flow diagram for forming a dielectric structure according to anembodiment of the present disclosure is shown in FIG. 3, and includesthe step 302 of forming a dry-etch-resistant photopolymer layer on asubstrate. In an embodiment, the dry-etch-resistant photopolymer is afluorinated photopolymer composition that includes a first repeatingunit having a fluorine-containing group, a second repeating unit havinga photo cross-linkable group and a third repeating having adry-etch-resistant group containing one or more dry-etch-resistantatoms, as discussed previously.

In step 304 the dry-etch-resistant photopolymer layer is exposed toradiation within the spectral sensitivity range of the photopolymer(e.g., light in a range of 300 nm to 450 nm), thereby forming an exposeddry-etch-resistant photopolymer layer. In an embodiment, the exposure isa blanket exposure and all areas are exposed. In an alternativeembodiment, the radiation is patterned thereby forming an exposeddry-etch-resistant photopolymer layer having both exposed and unexposedportions. Methods for providing patterned radiation are discussed above.

In the case where radiation from step 304 is patterned, a developedstructure is formed in step 306 that includes a first pattern of exposeddry-etch-resistant photopolymer. This can be done by contacting theexposed dry-etch-resistant photopolymer layer to a developing agent in amanner previously discussed with respect to step 6. During development,the portions of unexposed photopolymer are removed, thus forming adeveloped structure having a first pattern of exposed dry-etch-resistantphotopolymer that covers the substrate and a complementary secondpattern of uncovered substrate corresponding to the removed portion ofphotopolymer.

In Step 308, the exposed dry-etch-resistant photopolymer or thedeveloped structure is treated with a dry etching gas to form a firstdielectric structure having a surface region comprising a higher densityof dry-etch-resistant atoms than an interior region of the polymer. Inan embodiment, the interior region also has a higher density of fluorineatoms than the surface region. In an embodiment, the dry-etch-resistantatom is Si and the dry etch is oxygen-based, thereby forming a surfaceregion that is higher in silicon as silicon oxide relative to aninterior region closer to the substrate, and an interior region that ishas higher density of fluorination than the surface region. If the dryetching gas is treating a developed structure, the step may be used topattern etch a portion of the uncovered substrate, e.g., a layer of anactive organic material, in addition to forming a first dielectricstructure.

The embodiment of FIG. 3 is illustrated in FIGS. 4A-4D as a series ofcross-sectional views, in this case using a developed structure. In FIG.4A, a dry-etch-resistant photopolymer layer 443 is shown provided over asubstrate 440 having a support 441 and a layer of active organicmaterial 442, e.g., an organic semiconductor.

In FIG. 4B, the dry-etch-resistant photopolymer 443 is exposed topatterned radiation by providing a photomask 445 and a source ofradiation 444, e.g., UV radiation. This forms an exposed photopolymerlayer 446 having a first pattern of cross-linked photopolymer 447 and acomplementary second pattern of unexposed photopolymer 448.

In FIG. 4C, a developed structure 401 is shown that is formed bycontacting the exposed photopolymer layer 446 with a developing agentcomprising a fluorinated solvent to remove the second pattern ofunexposed photopolymer 448, leaving behind a first pattern of developedphotopolymer 449 covering the active organic material layer 442 and acomplementary second pattern of uncovered substrate 450. The firstpattern of developed photopolymer 449 corresponds to the first patternof cross-linked photopolymer 447, and the second pattern of uncoveredsubstrate 450 corresponds to the second pattern of unexposedphotopolymer 448, although the shapes may not be identical due todevelopment/exposure effects. Further, in the present embodiment, thefirst pattern of developed photopolymer 449 is shown having outwardlysloping side walls 449B relative to the top surface 449A. In otherembodiments, the sidewalls could be vertical, straight, curved, orinwardly sloping. The shape of the sidewalls is a function of the degreeof cross-linking and development rate.

In FIG. 4D, a structure is shown after treatment with a dry etch gas455. The etch gas has removed the active organic material in portionscorresponding to the second pattern of uncovered substrate leaving alayer of patterned active organic material 451. The etch gas treatmentforms a dielectric structure 452 having a surface region 453 comprisinga higher density of dry-etch-resistant atoms than an interior region454. In the present embodiment, both the top surface 449A and sidewalls449B of the developed photopolymer have the higher density ofdry-etch-resistant atoms. In other embodiments, e.g., where thesidewalls are vertical or slope inwardly, it may be that only the topsurface has the higher density. Although surface region 453 and interiorregion 454 are shown as discrete portions or layers, the density ofdry-etch-resistant atoms may instead have a gradient without a discreteboundary. In an embodiment, the surface region 453 has a high content ofsilicon oxide. In an embodiment, the surface region 453 has reducedfluorine content relative to the interior region 454 and improvedadhesion to subsequently-applied layers. The dielectric structure mayoptionally be substantially transparent to visible light. In anembodiment, the dielectric structure has a permittivity in a range of 2to 5.

FIG. 5 is a cross-sectional diagram of OTFT device 500 that may beprepared by combining some of the methods and structures discussedabove. In FIG. 5, source 516 and drain 518 electrodes are provided overa support 541. A patterned organic semiconductor layer 551 covers thesource and drain electrodes and a portion of the support 541. A firstdielectric structure 552 is provided over the patterned organicsemiconductor 551. The first dielectric structure 552 comprises asurface region 553 having a higher density of dry-etch-resistant atomsthan an interior region 554. Gate electrode 520 is provided over firstdielectric structure 552 which acts as a gate dielectric layer in thistop gate, bottom contact OTFT structure.

A second dielectric structure 562 is provided over the first dielectricstructure 552 and the exposed edge of the patterned organicsemiconductor layer 551. The second dielectric structure 562 comprises asurface region 563 having a higher density of dry-etch-resistant atomsthan an interior region 564. The second dielectric structure acts as abarrier layer that protects the OTFT device, e.g., from moisture. In anembodiment, surface regions 553 and 563 have a high content of siliconoxide.

Many variations of the above embodiment are possible. For example, thegate dielectric layer may include first and second stacked dielectricstructures with the gate electrode over the second dielectric. Thebarrier layer may comprise multiple layers of dielectric structures. Inan embodiment, the water vapor transmission rate through a barrier layercomprising the present dielectric structure is less than 10⁻⁵ g/m²/day,preferably less than 10⁻⁶ g/m²/day, under ambient temperature andhumidity conditions. In an embodiment, the water vapor transmission ratethrough a barrier comprising the present dielectric structure is lessthan 10⁻² g/m²/day, preferably less than 10⁻³ g/m²/day, in anaccelerated test at 60° C./90% RH (relative humidity).

A bioelectronic device such as a biosensor, an ion pump, anelectrochemical transistor, a drug delivery device and the like may usethe present fluorinated photopolymer or dielectric structure as one ormore structural or barrier layers. In some embodiments, e.g.,implantable bioelectronic devices, such structural or barrier layers maybe particularly beneficial.

Examples

Photopolymer Compositions 1-6

Synthesis of 2-cinnamoyloxyethyl methacrylate (Compound C-8)

With ice bath cooling, a solution of 8.3 g (0.05 mol) cinnamoyl chlorideand 10 mL of dry dimethylacetamide was slowly added to a stirredsolution of 6.5 g (0.05 mol) 2-hydroxyethyl methacrylate and 14 mL ofdry pyridine. When the addition was complete, the cooling bath wasremoved and the mixture warmed to ambient temperature over 3 hours.Water and ethyl acetate were added to the reaction mixture and theproduct was extracted into the organic layer. The organic layer waswashed successively with IN hydrochloric acid solution, saturated sodiumbicarbonate solution and saturated sodium chloride solution, then driedover magnesium sulfate, and filtered. The solvent was removed undervacuum to give 12.1 g (93% of theoretical 13.0 g) of the monomer as aclear, yellow oil. NMR was used to verify the composition. The monomerwas used without further purification in the polymerization step.

Synthesis of Photopolymer Composition 1

A clean, dry 250 mL, four-neck jacketed reactor was equipped with aTeflon-blade mechanical stirrer, a reflux condenser having a bubbleroutlet, a nitrogen inlet (the height of which can be adjusted to bebelow the surface of the reaction solution), and a programmable constanttemperature bath (CTB) attached to the reactor jacket. The reactor wascharged with FOMA (21.750 g, 50.326 mmol), compound C-8 (9.174 g, 35.247mmol), methacryloxypropyltris(trimethylsiloxy)silane (compound PR-3,6.402 g, 15.140 mmol), AIBN (0.2005 g, 1.22 mmol.) and Novec™ 7600solvent (119 g). The nitrogen inlet was placed below the surface of thesolution, and with good stirring, the reaction solution was sparged withnitrogen for 1 hour. During the nitrogen sparge, the CTB was pre-warmedto 62° C. with flow to the reactor jacket turned off. When the spargewas complete, the gas inlet tube was raised above the solution level andthe nitrogen flow was reduced to maintain a slight positive flow throughthe system during the reaction. The valves between the pre-heated CTBand the reactor were opened and the reaction solution was stirred withheating for 4.5 hours. The reaction mixture was cooled to 50° C. anddrained from the reactor. Several portions of Novec™ 7600 solvent wereused to rinse the reactor and these rinses were combined with theproduct solution that gave a total weight of 303.90 g (12.0 wt % polymersolution). The polymer was sensitized to hi-line UV radiation bydissolving 2,4-diethyl-9H-thioxanthen-9-one (4.5 wt % relative to thedry weight of the polymer in solution) in the polymer solution. Thesensitized polymer solution was filtered repeatedly using nitrogenpressure through a 0.05 micrometer cartridge filter to provide aparticle-free solution for coating. The fluorine content of thephotopolymer in Photopolymer Composition 1 was 33.3% by weight.

Synthesis of Photopolymer Composition 2

A clean, dry 40 mL vial was equipped with a magnetic stirrer, a nitrogeninlet that can be adjusted to be below the surface of the reactionsolution, and a nitrogen outlet attached to a bubbler. The vial wascharged with FOMA (1.8170 g, 4.20 mmol), compound C-8 (1.0387 g, 3.99mmol) compound PR-3 (0.6405 g, 1.51 mmol), ethyleneglycol dimethacrylate(“EGDMA” 0.0214 g, 0.11 mmol), dodecanethiol (“DT” 0.0213 g, 0.11 mol),AIBN (0.0192 g, 0.12 mmol) and Novec™ 7600 solvent (14 g). The nitrogeninlet was placed below the surface of the solution and with goodstirring the reaction solution was sparged with nitrogen for 30 minutes.When the sparge was complete the gas inlet tube was raised above thesolution level and the nitrogen flow was reduced to maintain a slightpositive flow through the system during the reaction. The vial wasplaced in a programmable oil-bath and the temperature was raised to 63°C. After heating for 4.5 hours, the reaction mixture was cooled toambient temperature and diluted with Novec™ 7600 to give a total weightof 29.3651 g (15.88 wt % polymer solution). The photopolymer in thisexample is a branched polymer. The EGDMA provided branching points andDT was used as a chain transfer agent to control molecular weight. Thepolymer was sensitized to h,i-line UV radiation by dissolving2,4-diethyl-9H-thioxanthen-9-one (4.5 wt % relative to the dry weight ofthe polymer in solution) in the polymer solution. The sensitized polymersolution was filtered repeatedly using nitrogen pressure through a 0.22micrometer cartridge filter to provide a particle-free solution forcoating. The fluorine content of the photopolymer in PhotopolymerComposition 2 was 29.5% by weight.

Synthesis of 2-(4-perfluorohexylethyl-3-methoxycinnamoyloxy)ethylmethacrylate (Compound C-1)

As a first step, perfluorohexylethyl triflate was prepared by thefollowing procedure. A solution of perfluorohexyl ethyl alcohol (10.05g, 0.0276 mol), triethylamine (4.7 mL, 3.41 g, 0.0337 mol), and 40 mL ofdry dichloromethane was cooled in an acetone/ice bath. A solution oftrifluoromethanesulfonic anhydride, (9.03 g, 0.0320 mol) and 20 mL ofdry dichloromethane was added in a drop-wise manner at a rate such thatthe reaction temperature remained below 2° C. When the addition wascomplete, the cooling bath was removed and the reaction mixture wasstirred at ambient temperature for 16 hours. The reaction mixture wasthen diluted with more dichloromethane and washed successively with 0.5N HCl solution, saturated sodium bicarbonate solution, saturated sodiumchloride solution and then dried over magnesium sulfate. The solvent wasremoved under vacuum while keeping the temperature to ambient or below,to give 13.9 g (101%) of a red oil that solidified when cooled. Thecomposition was checked by 1H-NMR and showed the desired product alongwith trace contamination by triethylamine. This material was suitablefor use in the fluoroalkylation reactions described below.

Next, 4-perfluorohexylethyl-5-methoxybenzaldehyde was prepared asfollows. To a solution of 4-hydroxy-3-methoxybenzaldehyde (vanillin,3.25 g, 0.0214 mol) and EtOAc, (20 mL) were added tetrabutylammoniumbromide (0.1056 g, 0.327 mmol), powdered potassium carbonate (3.0295 g,0.02192 mol) and perfluorohexylethyl triflate (11.68 g, 0.0235 mol). Theresulting slurry was stirred at ambient temperature for 16 hours. Thereaction mixture was diluted with more EtOAc and washed twice with 5%sodium hydroxide solution to remove trace of unreacted startingbenzaldehyde, then successively with 0.5 N HCl solution, saturatedsodium bicarbonate solution, saturated sodium chloride solution and thendried over magnesium sulfate. The solvent was removed under vacuum togive the desired product as a waxy solid. The composition was checked by1H-NMR.

As a next step, 4-perfluorohexylethyl-3-methoxycinnamic acid wassynthesized by the following procedure. A slurry of4-perfluorohexylethyl-5-methoxybenzaldehyde (11.7 g, 0.0235 mol),malonic acid (5.0 g, 0.048 mol), pyridine (5 mL, 4.9 g, 0.062 mol) andpiperidine (0.54 g, 6.34 mmol) was heated to 82° C. and stirred for 30minutes while degassing occurred. The reaction mixture was then heatedto 112° C. and stirred for a further 2 hours to complete the reaction.After cooling to ambient temperature, water (30 mL) was slowly added tothe reaction mixture to precipitate a thick slurry. With ice-watercooling, concentrated hydrochloric acid (5 mL) was added slowly toacidify the slurry to a pH of about 1. The reaction mixture was filteredand washed with water until the pH of the washes was neutral. The solidwas dried in a 50° C. vacuum oven for 16 hours and 10.5 g (91%) of solidwas recovered. The melting point was determined to be 138-140° C. and1H-NMR was used to verify composition. The purity of the product wassuitable for use in the next reaction.

Next, oxaloyl chloride (4.99 g, 39.3 mmol) was slowly added to an icecooled solution of 4-perfluorohexylethyl-3-methoxycinnamic acid (17.0 g,31.5 mmol), 30 mL dry THF and 2.8 g dry dimethylacetamide. Foaming inthe reaction mixture was controlled by adjusting the addition rate. Whenthe addition was complete, the reaction mixture was stirred with coolingfor 30 minutes and then warmed slowly to 40° C. After about 30 minutesthe outgassing had stopped and the reaction mixture was cooled toambient temperature. The solvent was removed under vacuum to give theacid chloride as a tan, solid residue. The yield was theoreticalincluding the dimethylacetamide used in the reaction. The product wasused in the next stage of the reaction without further purification.

The target monomer, compound C-1, was then prepared as follows. Asolution of 2-hydroxyethyl methacrylate (4.1 g, 31.5 mmol) and drypyridine, (10 mL) was cooled with an ice bath and4-perfluorohexylethyl-3-methoxycinnamoyl chloride (19 g, 31.5 mmol) wasadded in portions with cooling between each addition. Dimethylacetamide(10 mL) was used to rinse the flask and it was then added to thereaction mixture. The cooling bath was removed and the reaction mixturewas stirred at ambient temperature for 16 hours. Water (100 mL) wasadded to the reaction mixture with ice cooling. The product wasextracted into diethyl ether (100 mL). The aqueous layer was removed andthe ether layer was washed twice with IN hydrochloric acid solution (75mL), saturated sodium bicarbonate solution (75 mL) and then withsaturated sodium chloride solution (75 mL). The organic layer was driedover magnesium sulfate, filtered and the solvent was removed undervacuum. Care must be used when removing the solvent to control foaming.A total of 15.6 g of a deep-red oil, was recovered (76% of 20.5 gtheoretical yield). The composition was verified by 1H-NMR and thepurity was acceptable for use as a polymerizable monomer.

Synthesis of Photopolymer Composition 3

A solution of compound C-1 (3.12 g, 4.79 mmol), FOMA (2.17 g, 5.02mmol), AIBN (0.0216 g, 0.13 mmol) and trifluorotoluene (23.44 g) wassparged with nitrogen for 30 minutes and then heated to 63° C. for 4.5hours. After cooling to ambient temperature, the reaction mixture wasprecipitated in cold methanol (50 mL), washed twice with cold methanoland then dried at 50° C. under reduced pressure to give the copolymer asan orange solid. A solution of this polymer was prepared by dissolving1.0036 g in 9.0172 g of Novec™ 7600 solvent. No sensitizing dye wasadded. The solution was spin-coated on Si-wafer at 1000 rpm. Theresulting film had a thickness of approximately 0.75 μm. The fluorinecontent of the photopolymer in Photopolymer Composition 3 was 50.9% byweight.

Synthesis of Photopolymer Composition 4

In a manner similar to that used for Photopolymer Composition 3,Photopolymer Composition 4 was prepared including a photopolymer havinga FOMA/C-1 mole % ratio of 30/70, respectively, and a fluorine contentof 46.8% by weight.

Synthesis of Photopolymer Composition 5

In a manner similar to that used for Photopolymer Composition 3,Photopolymer Composition 5 was prepared including a photopolymer havinga FOMA/C-1 mole % ratio of 10/90, respectively, and a fluorine contentof 41.4% by weight.

Synthesis of Photopolymer Composition 6

In a manner similar to that used for Photopolymer Composition 1, aphotopolymer was prepared from four monomers:FOMA/C-8/PR-3/t-butylmethacrylate (TBMA) in a mole % ratio of40/35.1/15/9.9, respectively, having a fluorine content of 28.9% byweight. A coatable composition included Novec™ 7600 solvent and thesensitizer 2,4-diethyl-9H-thioxanthen-9-one at 4.5% by weight relativeto the dry weight of the photopolymer.

Coating and Performance of Photopolymer Compositions 1-6

The photopolymer compositions were individually spin-coated on 150 mmsilicon wafers that had been pre-primed with HMDS vapor and baked at 90°C. for 60 seconds. Film thicknesses were typically in a range of about0.5 to 2.0 μm when spun at 1000 rpm, but can be adjusted by spin speedor composition viscosity. The wafers were exposed to patterned actinicradiation at 365 nm wavelength at a series of increasing doses startingat 40 mJ/cm² to yield photo cross-linked polymers. In a test using apatterned mask, Photopolymer Compositions 1, 3, 4, 5 and 6 showedsubstantial cross-linking even at the lowest dose tried, 40 mJ/cm². Whendeveloped with Novec™ 7600. Compositions 1-4 yielded imaged films,although composition 5 did not clear well even in the low exposureareas, presumably due high photosensitivity. Photopolymer Composition 2required about 300 mJ/cm² to achieve cross-linking sufficient to fullywithstand sustained development in Novec™ 7600, but showed very good(sharp) line shape.

Film thickness after 60 sec development in Novec™ 7600 was determined asa function of exposure for Composition 1, 2 and 6 using a step tabletand uniform exposure (using a different exposure device than the oneabove). Table 1 shows the exposure dose that maintains 50% of the filmthickness after the 60 sec development (“0.5 speed point”). It alsoshows the slope of the thickness vs log(exposure dose) at the 0.5 speedpoint (“0.5 contrast”). One can see that Compositions 1 and 6 requirelower exposure dose than Composition 2 at the 0.5 speed point. On theother hand, the contrast of the branched polymer Composition 2 is abouttwice that of Compositions 1 and 6. Higher contrast often results insharper line shape, consistent with the observed patterning experimentabove.

TABLE 1 Photopolymer Composition 0.5 speed point (mJ/cm²) 0.5 contrast 114.9 0.43 2 179 1.06 6 15.5 0.58

The wettability of the fluorinated photopolymers can sometimes be animportant property to control. In some embodiments, an organic coatingmay be provided over a layer of fluorinated photopolymer. If the organiccoating solution has a contact angle that is too high on the layer offluorinated photopolymer (poor wettability), the coating may benon-uniform or bead up. It has been found that the contact angle ofmesitylene (an organic solvent) on fluorinated photopolymers of thepresent disclosure can be reduced by decreasing total fluorine weightpercentage or especially by adding branching. Table 2 shows contactangle of mesitylene on unexposed layers of Compositions 1, 2 and 6.

TABLE 2 Photopolymer Weight % F relative Mesitylene Composition topolymer Branching? contact angle 1  33% No 36° 2 29.5% Yes  8° 6 28.9%No 17°Photopolymer Composition 7

Photopolymer Composition 7 was prepared in a manner similar toPhotopolymer Composition 3 except that the photopolymer was formed fromthe monomers FOMA/C-1/PR-3 in a mole % ratio of 50/35/15, respectively,producing a photopolymer having a fluorine content of 42.8% by weight.No sensitizing dye was added. This composition was slightly cloudy evenafter filtration but still formed reasonable films. A film formed fromPhotopolymer Composition 7 was exposed to patterned actinic radiation at365 nm wavelength at a series of increasing doses starting at 40 mJ/cm².The pattern was developed by contact with two (2) 45 sec puddles ofHFE-6512. Exposure doses higher than 54 mJ/cm² produced sufficientcross-linking to form a patterned image.

Photopolymer Composition 8

Photopolymer Composition 8 was prepared in a manner similar toPhotopolymer Composition 3 except that the photopolymer was formed fromthe monomers FOMA/C-1/PR-3/IBMA (isobornyl methacrylate) in a mole %ratio of 50/30/10/10, respectively, producing a photopolymer having afluorine content of 42.8% by weight. No sensitizing dye was added. Thiscomposition was slightly cloudy even after filtration but still formedreasonable films. A film formed from Photopolymer Composition 8 wasexposed to patterned actinic radiation at 365 nm wavelength at a seriesof increasing doses starting at 40 mJ/cm². The pattern was developed bycontact with two (2) 45 sec puddles of HFE-6512. Even the lowestexposure of 40 mJ/cm² produced sufficient cross-linking to form apatterned image.

Photopolymer Composition 9

Photopolymer Composition 9 was like Photopolymer Composition 2 exceptthat no sensitizing dye was added. A film formed from PhotopolymerComposition 9 was exposed to patterned actinic radiation at 365 nmwavelength at a series of increasing doses starting at 40 mJ/cm² up to2.5 J/cm². When contacted with Novec™ 7600 no image formed, i.e., thereis insufficient cross-linking at 365 nm without a sensitizing dye toform a patterned image below 2.5 J/cm². Exposure to 254 nm radiationdoes cross-link the photopolymer without a sensitizing dye.

Photopolymer Composition 10

Photopolymer Composition 10 was like Photopolymer Composition 2 exceptthat a different sensitizing dye was added, 13FBNzph, at the same molarratio of dye to photopolymer.

A film formed from Photopolymer Composition 10 was exposed to patternedactinic radiation at 365 nm wavelength at a series of increasing dosesstarting at 40 mJ/cm². The pattern was developed by contact with Novec™7600. Exposure doses higher than 537 mJ/cm² produced sufficientcross-linking to form a patterned image. Although not as efficient as2,4-diethyl-9H-thioxanthen-9-one, 13FBNzph is an effective sensitizingdye.Photopolymer Composition 11

Photopolymer Composition 11 was prepared in a manner similar toPhotopolymer Composition 2 except that the photopolymer was formed fromthe monomers FOMA/C-8/PR-3/EGDMA/TX2CMA in a mole % ratio of46/36/15/1/5, respectively, producing a photopolymer having a fluorinecontent of 29.2% by weight. TX2CMA is a copolymerizable sensitizing dyehaving the structure shown below.

A film formed from Photopolymer Composition 11 was exposed to patternedactinic radiation at 365 nm wavelength at a series of increasing dosesstarting at 40 mJ/cm². The pattern was developed by contact with Novec™7600. Exposure doses higher than 124 mJ/cm² produced sufficientcross-linking to form a patterned image. Thus, this “attached”sensitizing dye is effective at sensitizing the cross-linking reactionat 365 nm.Photopolymer Composition 12

Photopolymer Composition 12 was prepared in a manner similar toPhotopolymer Composition 12 except that the photopolymer was formed fromthe monomers FOMA/C-8/PR-3/EGDMA/TX2CMA in a mole % ratio of46/31/10/1/10, respectively, producing a photopolymer having a fluorinecontent of 28.8% by weight. A film formed from Photopolymer Composition12 was exposed to patterned actinic radiation at 365 nm wavelength at aseries of increasing doses starting at 40 mJ/cm². The pattern wasdeveloped by contact with Novec™ 7600. Exposure doses higher than 204mJ/cm² produced sufficient cross-linking to form a patterned image.Although Composition 12 had more sensitizing dye than Composition 11, ithas slightly reduced photo cross-linking efficiency. This may be due tothe reduced amount of C-8.

Photopolymer Composition 13

Photopolymer Composition 13 was prepared in a manner similar toPhotopolymer Composition 1 except that the photopolymer was formed fromthe monomers FOMA/C-8 in a mole % ratio of 70/30, respectively,producing a photopolymer having a fluorine content of 45.4% by weight.Sensitizing dye 2,4-diethyl-9H-thioxanthen-9-one was added at 4.5% byweight relative to the photopolymer. A film formed from PhotopolymerComposition 13 was exposed to patterned actinic radiation at 365 nmwavelength at 1 J/cm². The pattern was readily developed by contact withtwo (2) 45 sec puddles of Novec™ 7600. Although exposure doses less thanthis were not tried, it is likely lower doses would be effective aswell.

Photopolymer Composition 14

Photopolymer Composition 14 was prepared in a manner similar toPhotopolymer Composition 1 except that the photopolymer was formed fromthe monomers FOMA/C-8 in a mole % ratio of 50/50, respectively,producing a photopolymer having a fluorine content of 35.6% by weight.Sensitizing dye 2,4-diethyl-9H-thioxanthen-9-one was added at 4.5% byweight relative to the photopolymer. A film formed from PhotopolymerComposition 14 was exposed to patterned actinic radiation at 365 nmwavelength at 1 J/cm². The pattern was readily developed by contact withtwo (2) 45 sec puddles of Novec™ 7600. Although exposure doses less thanthis were not tried, it is likely lower doses would be effective aswell.

Photopolymer Composition 15

Photopolymer Composition 15 was attempted to be prepared in a mannersimilar to Photopolymer Composition 1 except that the photopolymer wasformed from the monomers FOMA/C-8 in a mole % ratio of 30/70,respectively, producing a photopolymer having a fluorine content of23.7% by weight. However, this photopolymer was not sufficiently solublein Novec™ 7600 to prepare a useful coating solution. It is believed thatthe amount of fluorination was insufficient in this particular system,and in certain embodiments, the fluorine content should be at least 25%by weight relative to the photopolymer.

Photopolymer Compositions 16-18

Photopolymer Compositions 16-18 were prepared in a manner similar toPhotopolymer Composition 1 to provide a level series of dry-etchresistant monomer PR-3. In the case of Photopolymer Composition 16, thephotopolymer was formed from the monomers FOMA/C-8/PR-3 in a mole %ratio of 50.0/40.1/9.9, respectively, producing a photopolymer having afluorine content of 34.0% by weight. In the case of PhotopolymerComposition 17, the photopolymer was formed from the monomersFOMA/C-8/PR-3 in a mole % ratio of 49.8/34.8/15.4, respectively,producing a photopolymer having a fluorine content of 33.2% by weight.In the case of Photopolymer Composition 18, the photopolymer was formedfrom the monomers FOMA/C-8/PR-3 in a mole % ratio of 50.0/29.9/20.1,respectively, producing a photopolymer having a fluorine content of32.6% by weight. Rather than using 2,4-diethyl-9H-thioxanthen-9-one asthe sensitizing dye, trifluoromethylthioxanthone was used. In this case,sensitizing dye was sparingly soluble so that the compositions wereessentially saturated, but at an unknown specific concentration.

Films formed from these compositions were exposed to patterned actinicradiation at 365 nm wavelength at a series of increasing doses startingat 40 mJ/cm². The pattern was developed by contact with Novec™ 7600.Exposure doses higher than 390, 334 and 334 mJ/cm² produced sufficientcross-linking to form a patterned image in Compositions 16, 17 and 18,respectively. Even though the sensitizing dye was sparingly soluble, itwas effective at promoting cross-linking.

Films formed from these compositions were also studied to determinetheir etch resistance. These compositions, along with HPR-504, acommercially available photoresist from Fujifilm, were coated on Siwafers to form films having a thickness of about 1.2 μm. The films weresubjected to oxygen plasma (oxygen gas flow of 50 sccm, 100 mTorrvacuum, 100 W) in 30 sec increments and the film thicknesses werere-measured. The change in thickness from the previous measurement wasused to calculate an etch rate in nm/sec. The data are summarized inTable 3.

TABLE 3 Etch rates for HPR-504 and Photopolymer Compositions 16-18Polymer etch rates (nm/sec) calculated at various etch times AveComposition @ 30 sec @ 60 sec @ 90 sec @ 120 sec 60-120 sec HPR-504 316281 292 295 289 16 751 357 307 293 319 17 254 138 154 99 131 18 102 2614 75 38

From the data in Table 3, one can see that the conventional photoresistHPR-504 has a constant etch rate over 120 sec. Photopolymer Compositions16 through 18 show a different behavior. The initial etch rates (i.e., @30 sec) are substantially higher than they are at subsequent times. Theaverage etch rate for these films from 60 sec to 120 sec is roughly halfor less as compared to the 30 sec etch rate values. These observationsprovide evidence for the formation of a dielectric structure having asurface region that is higher in content of silicon oxide (lower incarbon & fluorine), which substantially slows the etch rate.

Photo cross-linked polymers of the present disclosure have been shown tobe resistant to strong organic solvents such as acetone and THF.

Representative Embodiments

Some non-limiting, representative embodiments of the present disclosureare described below.

Embodiment Group A

1. A photosensitive composition comprising:

a fluorinated photo cross-linkable polymer comprising at least arepeating unit having a fluorine-containing cinnamate group, wherein thepolymer has a total fluorine content in a range of 20 to 60% by weight;and

a fluorinated solvent.

2. The composition of embodiment 1 wherein the polymer comprises astructure according to formula (1):

wherein p is an integer from 1 to 5, X is an independently selectedfluorine-containing alkyl, alkoxy, alkylthio, aryl, aryloxy, alkanoate,benzoate, alkyl ester, aryl ester, or alkanone; q is an integer from 0to 4 such that q+p≤5, Z is an independently selected alkyl, alkoxy,alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester,or alkanone; and “poly” represents a polymer chain including anyoptional linking groups between the fluorinated cinnamate group and thepolymer chain.

3. The composition according to embodiment 2 wherein the weight percentof the structure according to formula (1), not including the weightcontribution from “poly”, accounts for at least 25% of the total polymerweight.

4. The composition according to any of embodiments 1-3 wherein thefluorinated solvent is a hydrofluoroether.

5. The composition according to embodiment 4 wherein thehydrofluoroether has a boiling point in a range of 100° C. to 175° C.

6. The composition according to any of embodiments 1-5 wherein the photocross-linkable polymer is formed from a polymerization reactionincluding one or more acrylate-based monomers.

7. The composition according to any of embodiments 1-6 wherein the photocross-linkable polymer further includes one or more alkyl-containingrepeating units.

8. A device comprising a layer formed from a fluorinated photocross-linkable polymer comprising at least a repeating unit having afluorine-containing cinnamate group, wherein the polymer has a totalfluorine content in a weight range of 20 to 60%.

9. The device according to embodiment 8 wherein the polymer comprises astructure according to formula (1):

wherein p is an integer from 1 to 5, X is an independently selectedfluorine-containing alkyl, alkoxy, alkylthio, aryl, aryloxy, alkanoate,benzoate, alkyl ester, aryl ester, or alkanone; q is an integer from 0to 4 such that q+p≤5, Z is an independently selected alkyl, alkoxy,alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester,or alkanone; and “poly” represents a polymer chain including anyoptional linking groups between the fluorinated cinnamate group and thepolymer chain.

Embodiment Group B

1. A photosensitive composition comprising:

a fluorinated photo cross-linkable polymer comprising a first repeatingunit having a fluorine-containing group but not a cinnamate group, and asecond repeating unit having a fluorine-containing cinnamate group,wherein the polymer has a total fluorine content in a range of 30 to 60%by weight; and

a fluorinated solvent.

2. The composition of embodiment 1 wherein the second repeating unitcomprises a structure according to formula (1):

wherein p is an integer from 1 to 5, X is an independently selectedfluorine-containing alkyl, alkoxy, alkylthio, aryl, aryloxy, alkanoate,benzoate, alkyl ester, aryl ester, or alkanone; q is an integer from 0to 4 such that q+p≤5, Z is an independently selected alkyl, alkoxy,alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester,or alkanone; and “poly” represents a polymer chain including anyoptional linking groups between the fluorinated cinnamate group and thepolymer chain.

3. The composition according to embodiment 2 wherein the mole ratio ofthe first repeating unit to the second repeating unit is in a range of0.1 to 10.

4. The composition according to embodiment 3 wherein the mole ratio ofthe first repeating unit to the second repeating unit is in a range of0.25 to 4.

5. The composition according to any of embodiments 1-4 wherein thefluorinated solvent is a hydrofluoroether.

6. The composition according to embodiment 5 wherein thehydrofluoroether has a boiling point in a range of 100° C. to 175° C.

7. The composition according to any of embodiments 1-6 furthercomprising a third repeating unit having a dry-etch-resistant group.

8. The composition according to embodiment 7 wherein thedry-etch-resistant group includes at least one Si atom.

9. The composition according to embodiment 7 or 8 wherein the mole ratioof the third repeating unit relative to the combined first and secondrepeating units is in a range of 0.1 to 1.

10. The composition according to any of embodiments 1-9 wherein thephoto cross-linkable polymer is formed from a polymerization reactionincluding one or more acrylate-based monomers.

11. A device comprising a layer formed from a photo cross-linkablepolymer comprising a first repeating unit having a fluorine-containinggroup but not a cinnamate group, and a second repeating unit having afluorine-containing cinnamate group, wherein the polymer has a totalfluorine content in a range of 30 to 60% by weight.

12. The device according to embodiment 11 wherein the second repeatingunit comprises a structure according to formula (1):

wherein p is an integer from 1 to 5, X is an independently selectedfluorine-containing alkyl, alkoxy, alkylthio, aryl, aryloxy, alkanoate,benzoate, alkyl ester, aryl ester, or alkanone; q is an integer from 0to 4 such that q+p≤5, Z is an independently selected alkyl, alkoxy,alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester,or alkanone; and “poly” represents a polymer chain including anyoptional linking groups between the fluorinated cinnamate group and thepolymer chain.

Embodiment Group C

1. A photosensitive composition comprising:

a fluorinated photo cross-linkable polymer comprising at least a firstrepeating unit having a fluorine-containing group and a second repeatingunit having a cinnamate group; and

a hydrofluoroether solvent.

2. The composition of embodiment 1 further comprising a third repeatingunit having a dry-etch-resistant group including at least onedry-etch-resistant atom having an atomic weight of at least 24.

3. The composition of embodiment 2 wherein the dry-etch-resistant atomis selected from the group consisting of Si, Ti, Ge, Al, Zr, and Sn.

4. The composition according to embodiment 2 or 3 wherein thedry-etch-resistant group includes at least one Si atom.

5. The composition according to any of embodiments 2-4 wherein the moleratio of the third repeating unit relative to the combined first andsecond repeating units is in a range of 0.1 to 1.

6. The composition according to any of embodiments 1-5 furthercomprising an additional repeating unit having a non-fluorinated alkylgroup in a mole ratio in a range of 0.05 to 0.25 relative to thecombined total of all other repeating units.

7. The composition according to any of embodiments 1-6 wherein the photocross-linkable polymer is formed from a polymerization reactionincluding one or more acrylate-based monomers.

8. The composition according to any of embodiments 1-7 wherein the photocross-linkable polymer has a total fluorine content in a range of 20 to55% by weight.

9. The composition according to embodiment 8 wherein the photocross-linkable polymer has a total fluorine content in a range of 25 to50% by weight.

10. The composition according to any of embodiments 1-9 wherein thehydrofluoroether has a boiling point in a range of 100° C. to 150° C.

11. The composition according to any of embodiment 1-10 wherein thesecond repeating unit comprises a structure according to formula (2):

wherein p is an integer from 0 to 5, X is an independently selectedfluorine-containing alkyl, alkoxy, alkylthio, aryl, aryloxy, alkanoate,benzoate, alkyl ester, aryl ester, or alkanone; q is an integer from 0to 5 such that q+p≤5, Z is an independently selected alkyl, alkoxy,alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester,or alkanone; and “poly” represents a polymer chain including anyoptional linking groups between the cinnamate group and the polymerchain.

12. The composition according to any of embodiments 1-11 wherein thecinnamate group does include any fluorinated groups.

Embodiment Group D

1. A method of processing a fluorinated photo cross-linkable polymer,comprising:

forming a photopolymer layer on a substrate, the photopolymer layerincluding a photo cross-linkable polymer according to any of EmbodimentGroups A, B or C;

exposing the photopolymer layer to patterned radiation to form anexposed photopolymer layer; and

contacting the exposed photopolymer layer with a developing agent toremove a portion of the exposed photopolymer layer in accordance withthe patterned light, thereby forming a developed structure having afirst pattern of cross-linked photopolymer covering the substrate and acomplementary second pattern of uncovered substrate corresponding to theremoved portion of polymer, the developing agent comprising at least 50%by volume of a fluorinated developing solvent.

2. The method according to embodiment 1 wherein the fluorinateddeveloping solvent is a hydrofluoroether.

3. The method of embodiment 1 or 2 wherein the substrate comprises anactive organic material layer in contact with the photopolymer layer.

4. The method of embodiment 3 further comprising the step of etching theactive organic material layer in the second pattern of uncoveredsubstrate wherein the first pattern of cross-linked photopolymer acts asan etch barrier.

5. The method of embodiment 4 wherein the etching includes a wet etchthat solubilizes the active organic material in the second pattern ofuncovered substrate.

6. The method of embodiment 4 wherein the etching includes a dry-etchthat removes the active organic material in the second pattern ofuncovered substrate.

Embodiment Group E

1. A method of forming a dielectric structure comprising:

providing a first photopolymer layer over a substrate, the firstphotopolymer layer comprising a first photo cross-linkable polymerhaving at least a first repeating unit having a fluorine-containinggroup, a second repeating unit having a photo cross-linkable group and athird repeating having a dry-etch-resistant group including at least onedry-etch-resistant atom having an atomic weight of at least 24;

exposing the first photopolymer layer to radiation to form across-linked first polymer; and

subjecting the cross-linked first polymer to a dry etching gas to form afirst dielectric structure having a surface region comprising a higherdensity of dry-etch-resistant atoms than an interior region.

2. The method according to embodiment 1 wherein the radiation ispatterned radiation that forms a first pattern of exposed polymer and acomplementary second pattern of unexposed polymer, and furthercomprising the step of contacting the exposed photopolymer layer with adeveloping agent comprising a fluorinated solvent to remove the secondpattern of unexposed polymer thereby forming a first developedstructure, such first developed structure comprising the cross-linkedfirst polymer that is subjected to the dry etching gas.

3. The method according to any of embodiments 1-2 further comprising:

providing a second photopolymer layer over the first dielectricstructure, the second photopolymer layer comprising a second photocross-linkable polymer having at least a first repeating unit having afluorine-containing group, a second repeating unit having a photocross-linkable group and a third repeating having a dry-etch-resistantgroup including least one dry-etch-resistant atom having an atomicweight of at least 24;

exposing the second photopolymer layer to second radiation to form across-linked second polymer; and

subjecting the cross-linked second polymer to a second dry etching gasto form a second dielectric structure having a surface region comprisinga higher density of dry-etch-resistant atoms than an interior region.

4 The method according to embodiment 3 wherein the second radiation ispatterned radiation that forms a third pattern of exposed second polymerand a complementary fourth pattern of unexposed second polymer, andfurther comprising the step of contacting the exposed secondphotopolymer layer with a developing agent comprising a fluorinatedsolvent to remove the fourth pattern of unexposed polymer therebyforming a second developed structure, such second developed structurecomprising the cross-linked second polymer that is subjected to thesecond dry etching gas.

5. The method according embodiment 3 or 4 wherein the second photocross-linkable polymer has substantially the same chemical compositionas the first photo cross-linkable polymer.

6. The method according to any of embodiments 1-5 wherein the substratecomprises an organic semiconductor layer and the first photopolymerlayer is provided in direct contact with the organic semiconductor.

7. The method according to any of embodiments 1-6 wherein at least onedielectric structure forms at least a portion of a gate dielectric in anorganic thin film transistor and has a permittivity in a range of 2 to5.

8. The method according to any of embodiments 1-7 wherein at least onedielectric structure acts as a moisture barrier having a water vaporpenetration rate of less than 10⁻⁵ g/m²/day under ambient temperatureand humidity conditions.

9. The method according to any of embodiments 1-8 wherein the photocross-linkable group of at least one photo cross-linkable polymer is anacid-catalyzed epoxy group or a non-acid-catalyzed cinnamate thatoptionally includes a fluorine substituent.

10. The method according to any of embodiments 1-9 wherein at least onedielectric structure forms a bank or well structure in a display device.

11. The method according to any of embodiments 1-9 wherein at least onedielectric structure forms a portion of a touch screen device.

12. The method according to any of embodiments 1-11 further comprisingpatterning a metal layer over at least one dielectric structure.

13. The method according to any of embodiments 1-12 wherein at least onephoto cross-linkable polymer has a total fluorine content in a weightrange of 15 to 60%.

14. The method according to any of embodiments 1-13 wherein the moleratio of the first repeating unit to the second repeating unit of atleast one photo cross-linkable polymer is in a range of 0.1 to 10.

15. The method according to embodiment 14 wherein the mole ratio of thefirst repeating unit to the second repeating unit of at least one photocross-linkable polymer is in a range of 0.25 to 4.

16. The method according to any of embodiments 1-15 wherein the moleratio of the third repeating unit relative to the combined first andsecond repeating units for at least one photo cross-linkable polymer isin a range of 0.1 to 1.

17. The method according to any of embodiments 1-16 wherein thedry-etch-resistant atom for at least one photo cross-linkable polymer isselected from the group consisting of Si, Ti, Ge, Al, Zr, and Sn.

18. The method according to any of embodiments 1-17 wherein thedry-etch-resistant group includes at least one Si atom.

19. A device comprising a dielectric structure formed according to anyof methods 1-18.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations, combinations, and modifications can be effected by a personof ordinary skill in the art within the spirit and scope of theinvention.

LIST OF REFERENCE NUMBERS USED IN THE DRAWINGS

-   2 form photopolymer layer on substrate step-   4 form exposed photopolymer layer step-   6 form developed structure step-   10 substrate-   12 organic semiconductor material layer-   14 gate dielectric material layer-   16 source electrode-   18 drain electrode-   20 gate electrode-   302 form dry-etch-resistant photopolymer layer on substrate step-   304 form exposed dry-etch-resistant photopolymer layer step-   306 optionally form developed structure step-   308 treat with dry etch gas step-   401 developed structure-   440 substrate-   441 support-   442 active organic material layer-   443 dry-etch-resistant photopolymer layer-   444 radiation-   445 photomask-   446 exposed photopolymer layer-   447 first pattern of cross-linked photopolymer-   448 second pattern of unexposed photopolymer-   449 first pattern of developed photopolymer-   449A top surface of developed photopolymer-   449B outwardly sloping sidewalls of developed photopolymer-   450 second pattern of uncovered substrate-   451 patterned active organic material layer-   452 dielectric structure-   453 surface region of dielectric structure-   454 interior region of dielectric structure-   455 dry etch gas-   500 OTFT device-   516 source electrode-   518 drain electrode-   520 gate electrode-   541 support-   551 patterned organic semiconductor layer-   552 first dielectric structure-   553 surface region of first dielectric structure-   554 interior region of first dielectric structure-   562 second dielectric structure-   563 surface region of second dielectric structure-   564 interior region of second dielectric structure

The invention claimed is:
 1. A photosensitive composition comprising: a fluorinated photo cross-linkable polymer comprising at least a first repeating unit having a fluorine-containing group, a second repeating unit having a cinnamate group and a third repeating unit having a dry-etch-resistant group including at least one dry-etch-resistant atom having an atomic weight of at least 24; and a hydrofluoroether solvent.
 2. The composition of claim 1 wherein the dry-etch-resistant atom is selected from the group consisting of Si, Ti, Ge, Al, Zr, and Sn.
 3. The composition of claim 1 wherein the dry-etch-resistant group includes at least one Si atom.
 4. The composition of claim 1 wherein the mole ratio of the third repeating unit relative to the combined first and second repeating units is in a range of 0.1 to
 1. 5. The composition of claim 1 further comprising an additional repeating unit having a non-fluorinated alkyl group in a mole ratio in a range of 0.05 to 0.25 relative to the combined total of all other repeating units.
 6. The composition of claim 1 wherein the photo cross-linkable polymer is an acrylate-based polymer.
 7. The composition of claim 1 wherein the photo cross-linkable polymer has a total fluorine content in a range of 20 to 55% by weight.
 8. The composition of claim 7 wherein the photo cross-linkable polymer has a total fluorine content in a range of 25 to 50% by weight.
 9. The composition of claim 1 wherein the hydrofluoroether has a boiling point in a range of 100° C. to 150° C.
 10. The composition of claim 1 wherein the second repeating unit comprises a structure according to formula (2):

wherein p is an integer from 0 to 5, X is an independently selected fluorine-containing alkyl, alkoxy, alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester, or alkanone; q is an integer from 0 to 5 such that q+p≤5, Z is an independently selected alkyl, alkoxy, alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester, or alkanone; and “poly” represents a polymer chain including any optional linking groups between the cinnamate group and the polymer chain.
 11. The composition of claim 1 wherein the cinnamate group does not include any fluorinated groups.
 12. A photosensitive composition comprising: a fluorinated photo cross-linkable polymer comprising at least a first repeating unit having a fluorine-containing group, a second repeating unit having a cinnamate group and an additional repeating unit having a non-fluorinated alkyl group in a mole ratio in a range of 0.05 to 0.25 relative to the combined total of all other repeating units; and a hydrofluoroether solvent.
 13. The composition of claim 12 wherein the photo cross-linkable polymer is an acrylate-based polymer.
 14. The composition of claim 12 wherein the photo cross-linkable polymer has a total fluorine content in a range of 20 to 55% by weight.
 15. The composition of claim 14 wherein the photo cross-linkable polymer has a total fluorine content in a range of 25 to 50% by weight.
 16. The composition of claim 12 wherein the hydrofluoroether has a boiling point in a range of 100° C. to 150° C.
 17. The composition of claim 12 wherein the second repeating unit comprises a structure according to formula (2):

wherein p is an integer from 0 to 5, X is an independently selected fluorine-containing alkyl, alkoxy, alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester, or alkanone; q is an integer from 0 to 5 such that q+p≤5, Z is an independently selected alkyl, alkoxy, alkylthio, aryl, aryloxy, alkanoate, benzoate, alkyl ester, aryl ester, or alkanone; and “poly” represents a polymer chain including any optional linking groups between the cinnamate group and the polymer chain.
 18. The composition of claim 12 wherein the cinnamate group does not include any fluorinated groups. 